1,1,3,3-Substituted hydroxyindanes

ABSTRACT

1,1,3,3-substituted hydroxyindanes of the formula ##STR1## wherein R 1  is selected from the group of hydrogen, halogen and optionally substituted alkyl, cycloalkyl, aralkyl and aryl and the group ##STR2## wherein X is sulphur or the group ##STR3## R 2  and R 3  can be the same or different and are selected from the group of hydrogen, halogen and optionally substituted alkyl, cycloalkyl, aralkyl and aryl group, or, if 
     R 2  and R 3  are in the ortho position to each other, they may form a condensed carbocyclic 5-membered ring together with the carbon atoms of the benzene ring to which they are attached as substituents, 
     R 4 , R 5 , R 6 , R 7 , R 8  and R 9  are the same or different and are selected from the group of optionally substituted alkyl, cycloalkyl, aralkyl and aryl or 
     R 4  and R 5  and/or R 6  and R 7  and/or R 8  and R 9  can form a cycloaliphatic ring together with the carbon atom to which they are attached as substituents or 
     R 6  and/or R 7  can also be hydrogen and 
     R 10  and R 11  can be identical or different and are selected from the group of hydrogen and optionally substituted alkyl or 
     R 10  and R 11  can form a cycloaliphatic ring together with the carbon atom to which they are attached as substituents. 
     The foregoing compounds are prepared by reacting an alkyl phenol in the presence of an acid catalyst at temperatures of from 100°-350° C. with an olefine.

This is a continuation of application Ser. No. 664,729, filed Mar. 8,1976, which, in turn, is a continuation of application Ser. No. 431,801,filed Jan. 8, 1974, now U.S. Pat. No. 3,954,889, issued May 4, 1976.

BACKGROUND

This invention relates to new 1,1,3,3-substituted hydroxyindanes and toprocesses for preparing them.

It is known that 4,6-diisopropyl-1,1-dimethyl-5-hydroxyindane can beprepared by reacting 2,6-isopropylphenol with isoprene in the presenceof an acid catalyst (British Pat. No. 1,199,695). It is also known that4-hydroxy-indanes can be prepared by a process of molecularrearrangement of chromans with molar quantities of aluminium chloride(U.S. Pat. No. 3,057,929).

These known processes, however, are not generally applicable and canonly be used for preparing the special hydroxyindanes mentioned above.

SUMMARY

New 1,1,3,3-substituted hydroxyindanes have now been found whichcorrespond to the following general formula ##STR4## in which R¹represents hydrogen, halogen or an optionally substituted alkyl,cycloalkyl, aralkyl or aryl group or the group ##STR5## in which Xrepresents sulphur or the group ##STR6## R² and R³ which may beidentical or different represent hydrogen, halogen or an optionallysubstituted alkyl, cyaloalkyl, aralkyl or aryl group or if R² and R³ arein the ortho-position to each other they form a condensed 5-memberedcarbocyclic ring with the C atoms substituted by them in the benzenering;

R⁴,R⁵,R⁶,R⁷,R⁸ and R⁹ may be identical or different and represent anoptionally substituted alkyl, cycloalkyl, aralkyl or aryl group; or

R⁴ and R⁵ and/or R⁶ and R⁷ and/or R⁸ and R⁹ may form a cycloaliphaticring, in each case together with the carbon atom which carries them assubstituents; or

R⁶ and/or R⁷ may also represent hydrogen; and

R¹⁰ and R¹¹ may be identical or different and represent hydrogen or anoptionally substituted alkyl group or

R¹⁰ and R¹¹ may form a cycloaliphatic ring together with the C atomwhich carries them as substituents.

DESCRIPTION

The halogens (R¹,R²,R³) may be fluorine, chlorine, bromine or iodine butchlorine and bromine are preferred.

The optionally substituted alkyl groups may be straight chain orbranched chain alkyl groups with up to 12 and preferably up to 8 carbonatoms and in particular up to 4 carbon atoms, for example methyl, ethyl,propyl, isopropyl, butyl, isobutyl, t.-butyl, amyl, isoamyl or theisomeric hexyl, heptyl or octyl groups.

The following are preferred: Methyl, ethyl, propyl, isopropyl, butyl,isobutyl, t.-butyl, amyl, isoamyl and hexyl groups.

The optionally substituted cycloalkyl groups may be groups with from 3to 8 carbon atoms, preferably the cyclopentyl or cyclohexyl group.

The optionally substituted aralkyl groups may be groups with up to 6carbon atoms in the aliphatic part and up to 14 carbon atoms in thearomatic part. The following are examples of the aliphatic part of thegroup: Methyl, propyl, isopropyl, butyl, isobutyl, pentyl and hexyl. Thearomatic part of the group may be phenyl, naphthyl or anthranyl. Thepreferred araliphatic groups are benzyl and ethylphenyl.

The optionally substituted aryl groups may be, for example, thefollowing: Phenyl, naphthyl or anthranyl; but phenyl is preferred.

Substituents on the optionally substituted groups R¹ to R⁹ may be, forexample, alkyl groups with up to 12 carbon atoms, preferably up to 6carbon atoms. They may be straight chain or branched, for examplemethyl, ethyl, propyl, isopropyl, butyl or t.-butyl.

It has also been found that these new 1,1,3,3-substituted hydroxyindanescan easily be prepared by reacting an alkylphenol of the general formula##STR7## in which

R¹² represents hydrogen, halogen or an optionally substituted alkyl,cycloalkyl, aralkyl or aryl group; and

R²,R³,R⁴ and R⁵ have the meanings indicated above and

y represents the integer 1 or 2 in the presence of an acid catalyst at atemperature of from 100° to 350° C. with an olefine in which at leastone carbon atom with a double bond is attached exclusively to a carbonatom that is to say the olefine contains the group ##STR8## or byreacting the compound of general formula II under these conditions witha compound which yields the corresponding olefin in situ.

The temperatures employed are preferably within the range of 110° to250° C., in particular from 120° to 180° C.

The acid catalyst used in the process according to the invention maygenerally be the same known acid catalysts as those used in known mannerfor alkylating phenols (see DAS No. 1 518 460, DOS No. 1 643 390, DOSNo. 2 034 369 and DOS No. 2 111 193).

The following are mentioned as examples of such catalysts: Lewis acidssuch as AlCl₃ and BF₃. Protonic acids, that is to say acids which giveup a proton when they dissociate, in particular mineral acids such assulphuric acid, phosphoric acid, hydrochloric acid and perchloric acid.Silicas and Fuller's earths such as Montmorrillonite, silicoaluminatesand silica gel. The silicas suitable for this purpose are finely dividedmaterials which contain silicic acid and/or aluminium oxide. Silicas andFuller's earths of this kind may either be used without a preliminarytreatment or they may first be activated with mineral acids such assulphuric acid, phosphoric acid, hydrochloric acid, perchloric acid orhydrofluoric acid. Natural or synthetic ion exchangers such as zeolitesor exchanger resins. These exchanger resins are insoluble resins whichconsist of inert two-dimensionally or three-dimensionally cross-linkedpolymers anions are substituted with reactive groups such as phosphoric,phosphonic, sulphuric or sulphonic acid groups.

The catalysts used in the process according to the invention arepreferably mineral acids, Fuller's earths, silicas and exchanger resins.

The preferred mineral acids are sulphuric acid, hydrochloric acid andphosphoric acid.

The silicas and Fuller's earths are preferably those which have beenactivated by acid treatment in known manner (Chemie fur Labor andBetrieb, 1956, page 422; Ullmann, 3rd Edition Volume 9, page 271 et seq;Volume 8, pages 801 to 804).

The following are specific examples of suitable ion exchanger resins:Styrene-divinylbenzene resins, crosslinked styrene resins, phenolformaldehyde resins and benzene formaldehyde resins. All of these arepreferably substituted with sulphonic acid groups. Resins which containone sulphonic acid group for every 0.5 to 2 monomer units of the resinare particularly suitable (Ullmann, 3rd Edition, Volume 8, pages 806 to822, in particular page 816; German Patent Specification No. 915 267).

The reaction may also be carried out with mixtures of the abovementioned catalysts.

The quantity of catalyst used in the process according to the inventionmay vary within a wide range. In general about 2 to 30% by weight,preferably 7 to 14% by weight, based on the quantity of alkylphenol ofFormula II are used.

The alkylphenols of the general formula II which are used as startingmaterials in the process according to the invention and in which y=1 areknown per se. The following are examples: o-, m- and p-isopropyl-phenol;o-, m- and p-cyclopentyl-phenol; o-, m- and p-cyclohexyl-phenol; o-, m-and p-isobutyl-phenol; 1-phenyl-1-(4-hydroxy-phenyl)-ethane;3-methyl-6-isopropyl-phenol; 3-methyl-5-isopropylphenol;2-ethyl-4-cyclohexyl-phenol; 2-methyl-4-isobutylphenol;2-chloro-4-isopropyl-phenol.

The alkylphenols of the general formula II in which y=2 are also alreadyknown. The following are specific examples: 3,5-Diisopropylphenol,3,5-dicyclopentyl-phenol, 3,5-di-sec.-butyl-phenol,3,5-dicyclohexyl-phenol, 3-isopropyl-5-cyclopentyl-phenol,3-cyclopentyl-5-sec.-butylphenol, 2,6-diisopropylphenol,2,6-dicyclopentyl-phenol, 2-isopropyl-6-cyclopentylphenol and3,4-diisopropylphenol.

Olefines which contain the group ##STR9## that is to say in which atleast one carbon atom which carries a double bond is linked only toother carbon atoms, in other words so-called tertiary olefines, are alsoalready known. The following are specific examples: 2-Methylpropene,2-methyl-butene-(1), 2-methyl-butene-(2), 2,3-dimethyl-butene-(1),2,3-dimethyl-butene-(2), 2-methyl-2-phenyl-propene-(1). 2-Methylpropene(isobutylene) is preferred.

The molar ratio of alkylphenol of the general formula II to tertiaryolefine may vary within wide limits. The phenol and olefine may be usedin approximately equimolar proportions but it is preferred to use about2 mols of olefine to 1 mol of phenol. Even more than 2 mols of olefineper mol of phenol may be used, in which case the phenol nucleus may alsobe substituted by one or more alkyl groups which correspond to thetertiary olefine used.

The process according to the invention may be carried out at normalpressure or at elevated pressures of up to 60 atmospheres, preferably upto 20 atmospheres.

The reaction is preferably carried out within a pressure range of from 1to 10 atmospheres.

The process according to the invention may also be carried out in aninert solvent or diluent, for example in aliphatic and aromatichydrocarbons, in particular hexane and heptane, benzene, toluene andxylene.

The process according to the invention is generally carried out byintroducing the alkylphenol of the general formula II, optionally in theform of a solution in an inert solvent, into a suitable reaction vessel,e.g. an autoclave, adding the selected catalyst, heating to the chosenreaction temperature, adding the olefine with stirring and then leavingthe mixture to react for about 0.5 to 5 hours with stirring.

After termination of the reaction, the reaction product is worked up inconventional manner by removing the catalyst from the reaction vessel inknown manner, e.g. by filtration, centrifuging or washing, depending onthe nature of the catalyst, and then isolating the reaction productsfrom the reaction mixture which is now free from catalyst, this beingalso carried out by known methods such as distillation orcrystallisation.

The process according to the invention can be carried out continuouslyin a homogeneous phase with fixed bed or fluidised bed catalysts.Various apparatus and methods of procedure suitable for carrying out theprocess of the invention are known in the art. The process according tothe invention may be illustrated by the following reaction scheme whichrepresents by way of example the reaction of p-isopropyl-phenol withisobutylene: ##STR10##

Particularly good yields can be obtained by using 2 mols of tertiaryolefine per mol of phenol as starting material. This proportion ofstarting materials is therefore generally preferred.

Instead of using a tertiary olefine, the process may also be carried outby using compounds which yield the corresponding olefine in situ in thecourse of the reaction, for example the corresponding alcohols ortertiary alkyl phenols.

Isobutanol, tertiary butanol and 2-methyl-butanol-(2) are examples ofalcohols which may be used as starting materials by this method insteadof the corresponding olefines.

Furthermore, the alkylphenols of the general formula II may also bereacted with phenols which are substituted with one or more tertiaryalkyl groups instead of with the corresponding tertiary olefine. Thetertiary olefine is then obtained in situ from the tertiary alkyl group.Thus, for example, the reaction of 4-isopropylphenol and 4-tert.-butylphenol by the process according to the invention yields not only thereaction product according to the invention, which is1,1,3,3-tetramethyl-5-hydroxyindane, but also phenol. This proves that4-tertiary butyl-phenol yields isobutylene in situ in accordance withthe following reaction scheme: ##STR11##

The following are examples of phenols which are substituted withtertiary alkyl groups: o-, m- and p-tert.-butylphenol;2,4-di-tert.-butylphenol; and 3,5-di-tert.-butylphenol.

According to a preferred embodiment of the process of the invention,alkylphenols of the general formula II which are substituted by one ormore tertiary alkyl groups, i.e. in which one or more of the groups R¹²,R² and R³ represent tertiary alkyl groups, may be used to serve both asalkylphenols of the general formula II and at the same time as thecorresponding tertiary olefine. The reaction according to the inventionin that case proceeds as an intramolecular reaction.

The alkylphenols of formula II which may be used for the processaccording to the invention may also be prepared by a one pot processfrom an optionally substituted phenol in a first reaction stage and thenimmediately converted in a second reaction stage into the hydroxyindanesby the process according to the invention. This process may, forexample, be carried out as follows: The optionally substituted phenol,optionally dissolved in an inert solvent, is introduced into thereaction vessel and then the catalyst is added. The olefine is thenadded with stirring in the course of about 0.5 to 5 hours, depending onthe size of the batch, at a temperature of from 40° to 100° C. and atnormal or elevated pressure, preferably at a pressure of up to about 60atmospheres and in particular up to about 10 atmospheres. and whenalkylation has been completed, the temperature is raised to the reactiontemperature selected for the process according to the invention. Thesame or some other olefine is then added in the second stage of theprocess by the general procedure described above and the processaccording to the invention is carried out.

If alkylphenols of the general formula II in which y=2 are used asstarting materials for the hydroxyindanes according to the invention,then the hydroxyindanes of formula I correspond in particular to thefollowing general formulae ##STR12## in which

R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹² have the meanings already indicatedabove; and

R¹³ and R¹⁴ which may be identical or different represent an optionallysubstituted alkyl, cycloalkyl, aralkyl or aryl group or from acycloaliphatic ring together with the carbon atom which carries them assubstituents.

The symbols R¹², R¹³ and R¹⁴ cover the same meanings as the groups R¹ toR¹¹ also as regards the substituents. A special group of the new1,1,3,3-substituted hydroxyindanes correspond substantially to thefollowing formula ##STR13## in which R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ andX are as just defined.

The compounds of the general formula V may be prepared in known mannerby reacting compounds of the general formula ##STR14## in which R², R³,R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are as just defined with sulphur dichloride oraldehydes or ketones of the general formula ##STR15## in which R¹⁰ andR¹¹ have the meanings indicated above.

The following are examples of aldehydes and ketones which may be used asstarting compounds for preparing the compounds according to theinvention which are represented by the general formula V: Formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, hexanal,heptanal, 2-ethylhexanal, acetone, methyl ethyl ketone, diethylketone,methylisopropylketone, diisopropylketone, methylisobutylketone,methyl-tert.-butylketone, diisobutylketone, cyclopentanone, andcyclohexanone.

The following are examples of starting compounds of the general formulaVI which may be used for preparing the compounds of the general formulaV and which are in turn 1,1,3,3-substituted hydroxyindanes according tothe invention and may be prepared by the process according to theinvention:

5-Hydroxy-1,1,3,3-tetramethyl-indane;

5-hydroxy-6-tert.-butyl-1,1,3,3-tetramethyl-indane;

5-hydroxy-1,1,3,3,7-pentamethyl-indane;

5-hydroxy-6-cyclopentyl-1,1,3,3-tetramethyl-indane;

4-hydroxy-1,1,3,3,6-pentamethyl-indane;

5-hydroxy-1,3,3-trimethyl-1-ethyl-indane;

4-hydroxy-1,1,3-trimethyl-3-phenyl-indane;

5-hydroxy-1,3,3-trimethyl-1-phenyl-indane;

5-hydroxy-1,1-pentamethylene-3,3-dimethyl-indane;

5-hydroxy-6-tert.-butyl-1,1-pentamethylene-3,3-dimethyl-indane;

5-hydroxy-6-chloro-1,1,3,3-tetramethyl-indane;

5-hydroxy-1,1,2,3,3-pentamethyl-indane;

5-hydroxy-6-chloro-1,1-pentamethylene-3,3-dimethyl-indane;

5-hydroxy-6-chloro-1,3,3-trimethyl-1-phenyl-indane;

4-hydroxy-5-tert.-butyl-1,1,3-trimethyl-3-phenyl-indane;

5-hydroxy-6-tert.-butyl-1,1,2,3,3-pentamethyl-indane;

5-hydroxy-6-cyclopentyl-1,1,2,3,3-pentamethyl-indane;

4-hydroxy-1,1,3,3,6,7-hexamethyl-indane; and

5-hydroxy-1,1,3,3,4,7-hexamethyl-indane.

The new compounds of formula V may be prepared by methods known forpreparing bis-phenols (see Ullman Enzyklopadie der technischen Chemie,3rd Edition, Volume 13, Munich, Berlin 1962, page 448). Thehydroxyindane of formula VI used as starting material is usuallydissolved in an inert solvent or emulsified with the aid of anemulsifier. The selected acid catalyst, e.g. hydrochloric acid,sulphuric acid, phosphoric acid or p-toluenesulphonic acid, and thecorresponding aldehyde or ketone of the general formula VII are thenadded and the reaction mixture is stirred for some time at an elevatedtemperature in the region of from 40° C. to 150° C., preferably from 80°to 120° C.

The acid catalysts described above may generally also be used. It isgenerally unnecessary to use an acid catalyst if the reaction is carriedout with sulphur chloride instead of a compound of the general formulaVII since sulphur dichloride itself as well as the hydrogen chlorideevolved act as catalysts.

After termination of the reaction, the reaction product whichprecipitates on cooling in the form of a solid is isolated in knownmanner, e.g. by filtration or by centrifuging. Depending on the natureof the catalyst used, it can be removed in known manner by washing, ifindicated after first converting it into a soluble salt by neutralizingit, or the catalyst optionally together with solvent may be removed bydistillation, e.g. in the case of hydrochloric acid.

As already mentioned above, the reaction may either be carried outsolvent-free or in a homogeneous phase using organic solvents such asglacial acetic acid and chlorinated hydrocarbon or in an aqueousemulsion. If sulphur dichloride is used as starting material instead ofcompounds of the general formula VII, the process may also be carriedout as already described (see loc.cit page 452).

The following are examples of the new 1,1,3,3-substituted hydroxyindanesof the formula V which can be obtained as described above:

Bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-methane;

2-methyl-1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-propane;

bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-sulphide;

2,2-bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-propane;

2,2-bis-[5-hydroxy-6-tert.-butyl-1,1,3,3-tetramethyl-indanyl-(4)]-propane;

bis-[5-hydroxy-6-tert.-butyl-1,1,3,3-tetramethyl-indanyl-(4)]-methane;

2-methyl-1,1-bis-[5-hydroxy-6-tert.-butyl-1,1,3,3-tetramethyl-indanyl-(4)]-propane;

1,1-bis-[5-hydroxy-6-tert.-butyl-1,1,3,3-tetramethyl-indanyl-(4)]-butane;

bis-[5-hydroxy-6-cyclopentyl-1,1,3,3-tetramethyl-indanyl-(4)]-methane;

2-methyl-1,1-bis-[5-hydroxy-6-cyclopentyl-1,1,3,3-tetramethyl-indanyl-(4)]-propane;

bis-[5-hydroxy-6-chloro-1,1,3,3-tetramethyl-indanyl-(4)]-methane;

1,1-bis-[5-hydroxy-6-chloro-1,1,3,3-tetramethyl-indanyl-(4)]-butane;

2-methyl-1,1-bis-[5-hydroxy-6-chloro-1,1,3,3-tetramethyl-indanyl-(4)]-propane;

bis-[5-hydroxy-1,3,3-trimethyl-1-phenyl-indanyl-(6)]-methane;

2,2-cis-[3-hydroxy-1,3,3-trimethyl-1-phenyl-indanyl-(6)]-propane;

bis-[5-hydroxy-1,1-pentamethylene-3,3-dimethyl-indanyl-(6)]-methane;

2-methyl-1,1-bis[5-hydroxy-1,1-pentamethylene-3,3-dimethyl-indanyl-(6)]-propane;

bis-[5-hydroxy-1,1-pentamethylene-3,3-dimethyl-6-tert.-butyl-indanyl-(4)]-methane;

bis-[5-hydroxy-1,1,3,3-tetramethyl-6-tert.-butyl-indanyl-(4)]-sulphide;

bis-[5-hydroxy-1,1,3,3-tetramethyl-6-cyclopentyl-indanyl-(4)]-sulphide;

bis-[5-hydroxy-1,1,3,3-tetramethyl-6-chloro-indanyl-(4)]-sulphide;

bis-[5-hydroxy-1,1-pentamethylene-3,3-dimethyl-indanyl-(6)]-sulphide;

bis-[5-hydroxy-1,1-pentamethylene-3,3-dimethyl-6-tert.-butyl-indanyl-(4)]-sulphide;

bis-[5-hydroxy-1,3,3-trimethyl-1-phenyl-indanyl-(6)]-sulphide;

2,2-bis-[4-hydroxy-1,1,3-trimethyl-3-phenyl-indanyl-(7)]-propane;

1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-cyclohexane;

1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-6-tert.-butyl-indanyl-(4)]-cyclohexane;

1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-cyclopentane;

1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-6-tert.-butyl-indanyl-(4)]-cyclopentane;

1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-6-chloro-indanyl-(4)]-cyclohexane.

The new hydroxyindanes are valuable intermediate products, particularlyfor the synthesis of insecticides, germicides or fungicides and they mayalso be used as aromatic substances and antioxidants (British Pat. Nos.1,199,695 and U.S. Pat. No. 2,057,929).

By virtue of their reducing action, the new hydroxy-indanes may be usedin known manner as developers in photographic materials and processes.

The new hydroxyindanes may be used in particular as reducing agents forphotographic materials used for dry methods of producing photographiccopies on a layer which consists mainly of light insensitive, reduciblesilver salts, reducing agents and a toner and optionally also alight-sensitive heavy metal compound and/or a polymethine sensitizer forspectrally sensitizing the light insensitive silver compound.

Materials and processes of this kinds have been described in, forexample, German Pat. Nos. 1,300,014, and 1,234,243, in U.S. Pat. Nos.3,457,075 and 3,619,237, in French Patent 2,037,847 and in Belgian Pat.Nos. 770,971, 771,274 and 771,730.

The acid activated Fuller's earth used in the following examples wasobtained from Sudchemie AG, Munich under the trade name "K 10 SF" andthe ionic exchanger was prepared in accordance with German Pat. No.915,267.

The abbreviations Mp. and Bp. denote melting point and boiling point andthe suffix after the abbreviation Bp. indicates the pressure in Torr.

EXAMPLE 1

112 g (2 mol) of isobutylene were pumped for one hour into 136 g (1 mol)of 4-isopropyl-phenol in 100 ml of toluene and 30 g of an acid activatedFuller's earth in an autoclave with stirring at 150° C. The reactionmixture was then stirred for 6 hours at 150° C. After removal of thecatalyst by filtration, 120 g of pure1,1,3,3-tetramethyl-5-hydroxyindane were obtained by fractionaldistillation; Bp₁₂ : 144° C.; Mp: 119° C. ##STR16##

EXAMPLE 2

112 g (2 mol) of gaseous isobutylene were introduced into 136 g (1 mol)of 3-isopropyl-phenol and 10 g of an acid activated Fuller's earth in aglass flask at 150° C. with stirring. Stirring was then continued forone hour at 150° C. After removal of the catalyst by suction filtrationthe product was worked up by fractional distillation. At bp₁₂ : 144° C.there were obtained 71 g of 1,1,3,3-tetramethyl-5-hydroxy-indane and atbp₁₂ : 149°-155° C. 63 g of a fraction from which 33 g of1,1,3,3-tetramethyl-5-hydroxy-6-tert.-butyl-indane were obtained byrecrystallisation from cyclohexane: m.p. 114° C. ##STR17##

EXAMPLE 3

160 g (2.65 mol) of isobutylene were introduced into 210 g (1.4 mol) of3-methyl-5-isopropyl-phenol and 21 g of an acid activated Fuller's earthas described in Example 2. Distillation yields at bp₁₂ : 142°-144° C. 52g of a fraction from which 24 g of1,1,3,3,6-pentamethyl-4-hydroxy-indane were obtained byrecrystallisation from petroleum ether; mp: 66° C. ##STR18## 121 g ofanother fraction which boils at bp₁₂ : 160°-170° C. yields 77 g of1,1,3,3,7-pentamethyl-5-hydroxy-indane, mp: 120° C., byrecrystallisation from petroleum ether. ##STR19##

EXAMPLE 4

150 g (1 mol) of 4-sec.-butyl-phenol and 10 g of an acid activatedFuller's earth were reacted with 112 g (2 mol) of isobutylene asdescribed in Example 2. The resulting crude mixture was fractionated ina 1 m column filled with glass bodies. At bp₁₂ : 155°-160° C. there areobtained 68 g of a fraction from which 48 g of1,3,3-trimethyl-1-ethyl-5-hydroxy-indane were obtained byrecrystallisation from petroleum ether; mp: 86° C. ##STR20##

EXAMPLE 5

68 g (0.5 mol) of 3-isopropyl-phenol, 15 g of an acid activated Fuller'searth and 118 g (1 mol) of α-methylstyrene were stirred at 150° C. for 5hours. After removal of the catalyst by suction filtration and of theisopropylbenzene formed in the reaction by distillation, the residue wasfractionated over a 60 cm laboratory column with filling bodies. Aviscous oil containing 90% of 1,1,3-trimethyl-3-phenyl-4-hydroxy-indanewas obtained at bp₀.3 : 133°-137° C. ##STR21##

Another fraction which boiled at bp₀.3 : 143°-144° C. yielded 18 g of asolid compound from which 12 g of1,3,3-trimethyl-1-phenyl-5-hydroxy-indane could be isolated byrecrystallisation from ligroin; mp. 98°-100° C. ##STR22##

EXAMPLE 6

176 g (1 mol) of 4-cyclohexyl-phenol, 12 g of an acid activated Fuller'searth and 112 g (2 mol) of isobutylene were reacted together and workedup as described in Example 5. At bp₁.2 : 144°-146° C. there wereobtained 49 g of a fraction from which 25 g of1,1-pentamethylene-3,3-dimethyl-5-hydroxyindane, bp: 104° C., could beisolated by recrystallisation from petroleum ether. ##STR23## 51.3 g ofa fraction which boiled at bp₁.2 : 154°-160° C. yield 21 g of1,1-pentamethylene-3,3-dimethyl-6-tert.-butyl-5-hydroxyindane, mp 151°C., after recrystallisation from petroleum ether. ##STR24##

EXAMPLE 7

1.4 g (0.66 mol) of 2-chloro-4-isopropyl-phenol, 20 g of an acidactivated Fuller's earth and 75 g (1.33 mol) of isobutylene were reactedtogether and worked up as described in Example 2. 41 g of1,1,3,3-tetramethyl-6-chloro-5-hydroxy-indane were obtained; bp₀.2 : 79°C.; mp 52° C. ##STR25##

EXAMPLE 8

68 g (0.5 mol) of 3-isopropyl-phenol, 10 g of an acid activated Fuller'searth and 70 g (1 mol) of 2-methylbutene-(2) were reacted and worked upas described in Example 5. A fraction which boiled at bp₁₂ : 159°-170°C. yielded 9.5 g of 1,1,2,3,3-pentamethyl-5-hydroxy-indane, mp: 149° C.,on recrystallisation from benzene. ##STR26##

EXAMPLE 9

150 g (1 mol) of 2-isopropyl-5-methylphenol and 30 g of an acidactivated Fuller's earth were introduced into an autoclave. 112 g (2mol) of isobutylene were pumped in at 250° C. with stirring and themixture was then stirred for a further 3 hours at 250° C. After removalof the catalyst by suction filtration, 23 g of1,1,3,3,6-pentamethyl-4-hydroxy-indane were obtained by fractionaldistillation.

EXAMPLE 10

136 g (1 mol) of 4-isopropyl-phenol and 30 g of an acid activatedFuller's earth were introduced into an autoclave. 112 g (2 mol) ofisobutylene were pumped in at 70° C. with stirring and the mixture wasthen stirred for 3 hours at this temperature. The temperature was thenraised to 150° C. and stirring was continued for 4 hours. The catalystwas removed by suction filtration and the filtrate subjected tofractional distillation. 96 g of 1,1,3,3-tetramethyl-5-hydroxy-indanewere obtained.

EXAMPLE 11

75 g of 2,6-di-tert.-butyl-4-isopropyl-phenol and 10 g of an acidactivated Fuller's earth were stirred in a glass flask at 150° C. for 4hours. 10.5 g of isobutylene were trapped in a deep cooling condenser.30.5 g of 1,1,3,3-tetramethyl-5-hydroxy-indane could be obtained fromthe reaction mixture by distillation after removal of the catalyst.

EXAMPLE 12

100 g of 2-tert.-butyl-4-isopropyl-phenol and 10 g of an acid activatedFuller's earth were stirred in a glass flask for 4 hours at 150° C. Theisobutane formed in the reaction was trapped in a deep coolingcondenser. After removal of the catalyst, 28 g of1,1,3,3-tetramethyl-5-hydroxy-indane could be obtained by fractionaldistillation from the reaction mixture in addition to 26 g of4-isopropylphenol.

EXAMPLE 13

136 g (1 mol) of 4-isopropyl-phenol and 3 g of concentrated H₂ SO₄ werereacted with 112 g (2 mol) of isobutylene at 150° C. as described inExample 2. The catalyst was removed by washing with water. 18 g of1,1,3,3-tetramethyl-5-hydroxy-indane were isolated by fractionaldistillation.

EXAMPLE 14

136 g (1 mol) of 4-isopropyl-phenol and 20 g of an aluminium silicatewere reacted with 112 g (2 mol) of isobutylene in a stirrer autoclave at180° C. 51 g of 1,1,3,3-tetramethyl-5-hydroxy-indane were obtained byfractional distillation after removal of the catalyst by suctionfiltration.

EXAMPLE 15

112 g (mol) of gaseous isobutylene were introduced into 136 g (1 mol) of4-isopropyl-phenol and 10 ml of borofluoride etherate at 80° C. withstirring. The reaction mixture was then stirred for one more hour at 80°C. and for 5 hours at 150° C. The catalyst was removed by washing withwater. 49 g of 1,1,3,3-tetramethyl-5-hydroxy-indane could be obtainedfrom the reaction mixture by fractional distillation.

EXAMPLE 16

112 g (2 mol) of gaseous isobutylene were introduced with stirring into136 g (1 mol) of 4-isopropyl-phenol and 30 g of an ion exchanger resinat 80° C. The reaction mixture was then stirred for one hour at 80° C.and 5 hours at 150° C. The catalyst was removed by suction filtration.21 g of 1,1,3,3-tetramethyl-5-hydroxy-indane could be obtained from thereaction mixture by fractional distillation.

EXAMPLE 17

100 g of isobutylene were pumped into 93 g of 3,5-diisopropyl-phenol and13 g of an acid activated Fuller's earth in a stirrer autoclave at 150°C. Stirring was then continued for 4 hours at 250° C. After removal ofthe catalyst, the substance which crystallised from the cold reactionmixture was removed by suction filtration and recrystallised fromligroin. 54 g of 2,3;4,5-bis-[1,1,3,3-tetramethyl-trimethylene]-phenolwere obtained in this way: Melting point 249°-251° C. ##STR27##

EXAMPLE 18

112 g of isobutylene were introduced with stirring into 198 g of1-phenyl-1-(4-hydroxy-phenyl)-ethane and 30 g of an acid activatedFuller's earth at 150° C. and the reaction mixture was then stirred atthis temperature for 5 hours. 34 g of1,3,3-trimethyl-1-phenyl-5-hydroxy-indane could be obtained bydistillation followed by recrystallisation.

EXAMPLE 19 150 g of tert.-butanol were introduced dropwise into 136 g (1mol) of 4-isopropyl-benzene, 200 ml of benzene and 30 g of an acidactivated Fuller's earth with stirring and removal of water byazeotropic distillation. 36 g of water were separated. The isobutaneformed in the reaction was collected in a deep cooling condenserattached to the apparatus. After removal of the catalyst by suctionfiltration, 85 g of 1,1,3,3-tetramethyl-5-hydroxy-indane were obtainedby fractional distillation. EXAMPLE 20

68 g (1/2 mol) of 4-isopropyl-phenol, 150 g (1 mol) of4-tert.-butyl-phenol and 30 g of an acid activated Fuller's earth werestirred for 5 hours at 150° C. The substance which collected in the deepcooling condenser was isobutane. After removal of the catalyst bysuction filtration, fractional distillation yielded 46 g of1,1,3,3-tetramethyl-p-hydroxy-indane in addition to phenol.

EXAMPLE 21

38 g of 1,1,3,3-tetramethyl-5-hydroxyindane in 150 ml of benzene and 6.4ml of sulphur dichloride were stirred for 3 hours at 50° C. The crystalsobtained on cooling were suction filtered, dried and recrystallised fromchloroform. 21 g (51% of the theory) ofbis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-sulphide were obtained;Melting point 228°-230° C.

EXAMPLE 22

38 g of 1,1,3,3-tetramethyl-5-hydroxyindane, 300 ml of water, 6 ml of a10% Nersclat solution, 8 ml of concentrated hydrochloric acid and 30 mlof a 30% by weight aqueous formaldehyde solution were stirred for 6hours at 90° to 95° C. The crystals were precipitated on cooling weresuction filtered, dried and recrystallised from methanol. 16.6 g (43% ofthe theory) of bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-methane,melting point 207.5° C., were obtained.

EXAMPLE 23

22 g of isobutyraldehyde were slowly added to 114 g of1,1,3,3-tetramethyl-5-hydroxy-indane and 3 g of concentrated H₂ SO₄ at120° C. The temperature was lowered to 80° C. while the isobutyraldehydewas run in. The reaction mixture was then heated to 90° C. for 2 hours.It was then boiled up with 400 ml of benzene, 300 ml of water and 15 gof sodium acetate. Crystals precipitated from the separated benzenelayer on cooling. These were suction filtered, dried and recrystallisedfrom dioxane. 91.2 g (70% of the theoretical yield) of2-methyl-1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-propane,melting point 220° to 221° C., were obtained.

EXAMPLE 24

A mixture of 38 g of 1,1,3,3-tetramethyl-5-hydroxyindane, 300 ml ofwater, 7 ml of 10% by weight aqueous mersclat solution and 15 ml ofconcentrated hydrochloric acid and 20 g of isobutyraldehyde were stirredfor 6 hours at 90° to 95° C. The crystals which precipitated on coolingwere suction filtered, dried and recrystallised from dioxane. 40 g (92%of the theoretical yield) of2-methyl-1,1-bis-[5-hydroxy-1,1,3,3-tetramethyl-indanyl-(6)]-propane,melting point 220°-221° C. were obtained.

What is claimed is:
 1. 1,1,3,3-substituted hydroxy-indanes of theformula ##STR28## wherein R¹ is selected from the group of hydrogen,halogen and optionally substituted alkyl having up to 12 carbon atoms,cycloalkyl with 3 to 8 carbon atoms, aralkyl with up to 6 carbon atomsin the alkyl part and up to 14 carbon atoms in the aryl part and phenyl,naphthyl or anthranyl and the foregoing substituted by alkyl with up to12 carbon atoms; orR¹ is of the group ##STR29## wherein X is sulfur ofthe group ##STR30## R² and R³ can be the same or different and areselected from the group of hydrogen, halogen and optionally substitutedalkyl of up to 12 carbon atoms, cycloalkyl with 3 to 8 carbon atoms,aralkyl with up to 6 carbon atoms in the alkyl part and up to 14 carbonatoms in the aryl part, phenyl, naphthyl and anthranyl and the foregoingsubstituted by alkyl with up to 12 carbon atoms; or, if R² and R³ are inthe ortho position to each other, they can form a condensed carbocyclic5-membered ring together with the carbon atoms of the benzene ring towhich they are attached as substituents, R⁴, R⁵, R⁸ and R⁹ are the sameor different and are selected from the group of optionally substitutedalkyl with up to 12 carbon atoms, cycloalkyl with 3 to 8 carbon atoms,aralkyl with up to 6 carbon atoms in the alkyl part and up to 14 carbonatoms in the aryl part, phenyl, naphthyl and anthranyl or the foregoingsubstituted by alkyl with up to 12 carbon atoms; or R⁴ and R⁵ and/or R⁸and R⁹ can form a cycloaliphatic ring together with the carbon atom towhich they are attached as substituents; R⁶ and R⁷ are the same ordifferent and are selected from the group consisting of optionallysubstituted alkyl with up to 12 carbon atoms, cycloalkyl with 3 to 8carbon atoms, aralkyl with up to 6 carbon atoms in the alkyl part and upto 14 carbon atoms in the aryl part, phenyl, naphthyl, anthranyl and theforegoing substituted by alkyl with up to 12 carbon atoms, hydrogen orR⁶ and R⁷ can form a carbocyclic ring together with the carbon atom towhich they are attached as substituents; where any group of R¹ to R⁹ issubstituted it is substituted by an alkyl group of up to 12 carbon atomsand R¹⁰ and R¹¹ can be identical or different and are selected from thegroup of hydrogen and optionally substituted alkyl with up to 12 carbonatoms where the substituent is an alkyl group with up to 12 carbon atomsor R¹⁰ and R¹¹ can form a cycloaliphatic ring together with the carbonatom to which they are attached as substituents.
 2. A compound accordingto claim 1 which is 1,1,3,3-tetramethyl-5-hydroxyindane.
 3. A1,1,3,3-substituted hydroxyindane according to claim 1 wherein R⁶ and R⁷are hydrogen.
 4. A 1,1,3,3-substituted hydroxyindane according to claim1 wherein R¹, R² and R³ are hydrogen or halogen.
 5. A1,1,3,3-substituted hydroxyindane according to claim 3 wherein R¹, R²and R³ are hydrogen or halogen.
 6. 1,1,3,3-substituted hydroxyindanes ofthe formula ##STR31## wherein R¹ is selected from the group of hydrogenand optionally substituted alkyl having up to 12 carbon atoms,cycloalkyl with 3 to 8 carbon atoms, aralkyl with up to 6 carbon atomsin the alkyl part and up to 14 carbon atoms in the aryl part and phenyl,naphthyl or anthranyl and the foregoing substituted by alkyl with up to12 carbon atoms;R² and R³ can be the same or different and are selectedfrom the group of hydrogen and optionally substituted alkyl of up to 12carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aralkyl with up to 6carbon atoms in the alkyl part and up to 14 carbon atoms in the arylpart, phenyl, naphthyl and anthranyl and the foregoing substituted byalkyl with up to 12 carbon atoms; or if R² and R³ are in the orthoposition to each other, they can form a condensed carbocyclic 5-memberedring together with the carbon atoms of the benzene ring to which theyare attached as substituents; R⁴, R⁵, R⁸ and R⁹ are the same ordifferent and are selected from the group of optionally substitutedalkyl with up to 12 carbon atoms, cycloalkyl with 3 to 8 carbon atoms,aralkyl with up to 6 carbon atoms in the alkyl part and up to 14 carbonatoms in the aryl part, phenyl, naphthyl and anthranyl or the foregoingsubstituted by alkyl with up to 12 carbon atoms; or R⁴ and R⁵ and/or R⁸and R⁹ can form a cycloaliphatic ring together with the carbon atom towhich they are attached as substituents; R⁶ and R⁷ are the same ordifferent and are selected from the group consisting of optionallysubstituted alkyl with up to 12 carbon atoms, cycloalkyl with 3 to 8carbon atoms, aralkyl with up to 6 carbon atoms in the alkyl part and upto 14 carbon atoms in the aryl part, phenyl, naphthyl, anthranyl and theforegoing substituted by alkyl with up to 12 carbon atoms, hydrogen orR⁶ and R⁷ can form a carbocylic ring together with the carbon atom towhich they are attached as substituents; and where any group of R¹ to R⁹is substituted it is substituted by an alkyl group of up to 12 carbonatoms.
 7. Substituted hydroxyindanes according to claim 6 asfollows:1,1,3,3-Tetramethyl-5-hydroxy-indane,1,1,3,3-Tetramethyl-5-hydroxy-6-tert.-butyl-indane,1,1,3,3,6-Pentamethyl-4-hydroxy-indane,1,1,3,3,7-Pentamethyl-5-hydroxy-indane,1,3,3-Trimethyl-1-ethyl-5-hydroxy-indane, and1,1,2,3,3-Pentamethyl-5-hydroxy-indane.
 8. Substituted hydroxyindanesaccording to claim 6 as follows:1,1,3,3-Tetramethyl-5-hydroxy-indane,1,1,3,3-Tetramethyl-5-hydroxy-6-tert.-butyl-indane,1,1,3,3,6-Pentamethyl-4-hydroxy-indane,1,1,3,3,7-Pentamethyl-5-hydroxy-indane,1,3,3-Trimethyl-1-ethyl-5-hydroxy-indane,1,1,3-Trimethyl-3-phenyl-4-hydroxy-indane,1,3,3-Trimethyl-1-phenyl-5-hydroxy-indane, and1,1,2,3,3-Pentamethyl-5-hydroxy-indane.
 9. A substituted hydroxyindaneaccording to claim 6 wherein the substituted hydroxyindane is one of thegroup:1,1,3,3-Tetramethyl-5-hydroxyindane,1,1,3,3-Tetramethyl-5-hydroxy-6-tert.-butylindane,1,1,3,3,6-Pentamethyl-4-hydroxyindane,1,1,3,3,7-Pentamethyl-5-hydroxyindane and1,3,3-Trimethyl-1-ethyl-5-hydroxyindane.
 10. A substituted hydroxyindaneaccording to claim 6 wherein the substituted hydroxyindane is one of thefollowing:1,1,3,3-Tetramethyl-5-hydroxyindane,1,1,3,3-Tetramethyl-5-hydroxy-6-tert.-butylindane,1,1,3,3,6-Pentamethyl-4-hydroxyindane, 1.1,3,3,7-Pentamethyl-5-hydroxyindane,1,3,3-Trimethyl-1-ethyl-5-hydroxyindane,1,1,3-Trimethyl-3-phenyl-4-hydroxyindane and1,3,3-Trimethyl-1-phenyl-5-hydroxyindane.
 11. 1,1,3,3-substitutedhydroxyindanes of the formula ##STR32## wherein R¹ is selected from thegroup of hydrogen and optionally substituted alkyl having up to 12carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aralkyl with up to 6carbon atoms in the alkyl part and up to 14 carbon atoms in the arylpart and the foregoing substituted by alkyl with up to 12 carbonatoms;R² and R³ can be the same or different and are selected from thegroup of hydrogen and optionally substituted alkyl of up to 12 carbonatoms, cycloalkyl with 3 to 8 carbon atoms, aralkyl with up to 6 carbonatoms in the alkyl part and up to 14 carbon atoms in the aryl part, andthe foregoing substituted by alkyl with up to 12 carbon atoms; or if R²and R³ are in the ortho position to each other, they can form acondensed carbocyclic 5-membered ring together with the carbon atoms ofthe benzene ring to which they are attached as substituents; R⁴, R⁵, R⁸and R⁹ are the same or different and are selected from the group ofoptionally substituted alkyl with up to 12 carbon atoms, cycloalkyl with3 to 8 carbon atoms, aralkyl with up to 6 carbon atoms in the alkyl partand up to 14 carbon atoms in the aryl part, or the foregoing substitutedby alkyl with up to 12 carbon atoms; or R⁴ and R⁵ and/or R⁸ and R⁹ canform a cycloaliphatic ring together with the carbon atom to which theyare attached as substituents; R⁶ and R⁷ are the same or different andare selected from the group consisting of optionally substituted alkylwith up to 12 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aralkylwith up to 6 carbon atoms in the alkyl part and up to 14 carbon atoms inthe aryl part, and the foregoing substituted by alkyl with up to 12carbon atoms, hydrogen or R⁶ and R⁷ can form a carbocyclic ring togetherwith the carbon atom to which they are attached as substituents.